CN101878559A - Electrolytic composition and photoelectric conversion element using the same - Google Patents
Electrolytic composition and photoelectric conversion element using the same Download PDFInfo
- Publication number
- CN101878559A CN101878559A CN200880118419XA CN200880118419A CN101878559A CN 101878559 A CN101878559 A CN 101878559A CN 200880118419X A CN200880118419X A CN 200880118419XA CN 200880118419 A CN200880118419 A CN 200880118419A CN 101878559 A CN101878559 A CN 101878559A
- Authority
- CN
- China
- Prior art keywords
- electrolyte composition
- electrolyte
- cation
- durability
- sulfolane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
An electrolytic composition for a dye-sensitized solar cell contains an ionic liquid and a solvent. The solvent contains a content composed of at least sulfolane or a dielectric material of sulfolane. The amount of the content is 5 mass% to 40 mass% to the total amount of the electrolytic composition.
Description
Technical field
The present invention relates to electrolyte composition and the photo-electric conversion element that uses it.
The application based on November 30th, 2007 spy in Japanese publication be willing to require priority 2007-311352 number, its content is applied at this.
Background technology
Dye-sensitized solar cell is generally the structure by the reports such as M.Graetzel of Switzerland.This dye-sensitized solar cell has advantages such as conversion efficiency height, low cost of manufacture, as novel solar cell receive publicity (for example, with reference to patent documentation 1, non-patent literature 1).
Concise and to the point formation as dye-sensitized solar cell, on the electrode base board of transparent conductivity, possess the effect utmost point and with the setting of this effect utmost point subtend to electrode, this effect have by oxide semiconductor particulates (nano particle) such as titanium dioxide constitute and appendix the perforated membrane of light sensitizing coloring matter, be filled with the electrolyte that contains redox couple at these effect utmost points with between to electrode.This dye-sensitized solar cell is as making oxide semiconductor particulate sensitizing by the light sensitizing coloring matter that has absorbed incident lights such as sunlight, and the transform light energy that will comprise visible light is that the photo-electric conversion element of electric power plays a role.
For used in the past with the volatility electrolyte as solvent such as acetonitrile, when particularly waiting long-term use without, the volatilization of electrolyte takes place.Therefore, the battery behavior variation was difficult to guarantee as enough life-spans of element.In durability evaluation, for example,, under 85 ℃, 85%RH hygrothermal environment expose, under-40 ℃～90 ℃ the temperature cycles, require the stability more than 1000 hours for amorphous solar cell etc.To this, by fixedness and ionic liquid with high charge transport ability are applied to electrolyte, with the trial of the problem that solves solvent evaporates receive publicity (for example, with reference to non-patent literature 2).
In order to obtain the energy conversion efficiency height, the light sensitized solar cell that energy conversion efficiency does not also descend when using under hot environment, proposed to contain imidazole salts, greater than 10wt% and smaller or equal to the water of 50wt% or the electrolyte composition of alcohol and iodine (for example, with reference to patent documentation 2).
Patent documentation 1: specially permit communique No. 2664194
Patent documentation 2: the spy opens the 2002-289267 communique
Non-patent literature 1:M.Graetzel etc., Nature, (Britain),, No. 737, the 353rd page in 1991
Non-patent literature 2:N.Papageorgiou etc., J.Electrochem.Soc., (U.S.), 1996, the 143 (10) numbers, the 3099th page
Summary of the invention
But generally speaking, volatile solvents such as ionic liquid and acetonitrile are compared, the viscosity height, and therefore the charge transfer speed in electrolyte is slow, compares the problem that exists output to reduce when having used volatility electrolyte.The trial that ion liquid viscosity reduces is also in vogue, but being the material that possesses low viscosity and stability simultaneously, reality still is limited to a part, do not reach the levels of viscosity of above-mentioned volatility electrolyte.
In addition, also reported, pointed out that water might give various influences to the constituent material of element,, but guaranteed that durability may not be easy though initial performance improves by adding the ionic liquid that water has reduced viscosity.
And then, the trial that mixes other volatile solvents is also arranged, but still can not avoid the volatilization of solvent composition, particularly under the long duration test of above-mentioned strictness, be difficult to keep stable durability.
The present invention finishes in view of above-mentioned actual conditions, and its purpose is to provide the initial performance height, and the electrolyte composition of excellent in te pins of durability and the photo-electric conversion element that uses it.
The inventor is in order to solve above-mentioned problem, if for containing solvent in the electrolyte composition, then keep the become reason of difficulty of stable durability and further investigate repeatedly, the result thinks the volatility of solvent, and particularly its vapour pressure height might be a main cause.And the inventor is research repeatedly further, finds can solve above-mentioned problem by following invention.
Electrolyte composition of the present invention, it is the electrolyte composition that contains ionic liquid and solvent, above-mentioned solvent comprises at least one side's of containing sulfolane and derivative thereof the thing that contains, and with respect to the total amount of this electrolyte composition, this content that contains thing is 5 quality %～40 quality %.
Photo-electric conversion element of the present invention possesses above-mentioned electrolyte composition as electrolyte.
According to the present invention, the initial performance height is provided, and the electrolyte composition of excellent in te pins of durability and the photo-electric conversion element that uses it.
Description of drawings
Fig. 1 is the sectional view of an execution mode of expression photo-electric conversion element of the present invention.
Symbol description
1 dye-sensitized solar cell (photo-electric conversion element)
2 electrode base boards
5 appendix have the oxide semiconductor perforated membrane of pigment
The 6 effect utmost points
7 dielectric substrates
8 pairs of electrodes
Embodiment
Below the present invention is described in detail based on execution mode.
Electrolyte composition of the present invention, it is the electrolyte composition that contains ionic liquid and solvent, above-mentioned solvent comprises at least one side's of containing sulfolane and derivative thereof the thing that contains, and with respect to the total amount of this electrolyte composition, this content that contains thing is 5 quality %～40 quality %.
Ionic liquid as using among the present invention is not particularly limited, and can be the normal temperature fuse salt of liquid under the illustration room temperature.
As the cation of normal temperature fuse salt, can enumerate the salt that comprises imidazoles cation, pyrrolidines cation, pyridine cation, ammonium cation, Phosphonium cation, sulfonium cation etc.
As the imidazoles cation, for example can enumerate 1,3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation, 1-butyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-octyl group-3-methylimidazole cation, 1-decyl-3-methylimidazole cation, 1-ethyl-2,3-methylimidazole cation, 1-butyl-2,3-methylimidazole cation, 1-phenyl methyl-3-methylimidazole cation etc.
As the pyrrolidines cation, can enumerate for example 1-butyl-1-crassitude cation, 1-hexyl-1-crassitude cation, 1-octyl group-1-crassitude cation etc.
As the pyridine cation, can enumerate for example 1-ethylpyridine cation, 1-butyl-pyridinium cation, 1-hexyl pyridylium, 1-butyl-3-picoline cation, 1-butyl-4-picoline cation, 1-butyl-3,4-lutidines cation, 1-butyl-3,5-lutidines cation etc.
As the ammonium cation, can enumerate for example ethyl ammonium cation, butyl ammonium cation, tributyl ammonium cation, tetrapropylammonium cation, TBuA cation, trimethyl propyl ammonium cation etc.
Zuo Wei Phosphonium cation can be enumerated for example three hexyls (myristyl) phosphonium cation, 4-butyl-phosphonium cation, tributyl (2-methoxy ethyl) phosphonium cation etc.
As the sulfonium cation, can enumerate for example triethyl group sulfonium cation, tributyl sulfonium cation etc.
As the anion of normal temperature fuse salt, can enumerate and for example comprise iodide anion; two (trifluoromethyl sulfonyl) acid imide anion; two (fluorosulfonyl) acid imide anion; the dicyandiamide anion; thiocyanate radical (thiocyanic acid) anion; four cyano borate (four cyano boric acid) anion; tricyano methane anion; chloride anion; the bromide anion; hexafluoro-phosphate radical (hexafluorophosphoric acid) anion; tetrafluoroborate (tetrafluoro boric acid) anion; the dimethyl phosphate radical anion; the trifluoromethanesulfonic acid anion; the salt of ethyl sulphate (ethyl sulfuric acid) anion etc.
These salts can use a kind or will be more than 2 kinds mix and use.
As the solvent that uses among the present invention, comprise at least one side's of containing sulfolane and derivative thereof the thing that contains, the vapour pressure of this solvent is low more preferred more.Especially, the vapour pressure of sulfolane and derivative thereof is enough low, therefore can suppress solvent evaporates effectively, can keep stable durability.
As the sulfolane that contains in the solvent, be in particular thiophane 1,1-dioxide, tetramethylene sulfone.
Derivative as the sulfolane that contains in the solvent, be not particularly limited, preference such as 3-methyl sulfolane, 2, the 4-dimethylsulfolane, 2-fluoro sulfolane, 3-fluoro sulfolane, 3,4-fluoro sulfolane, 2,2,4-fluoro sulfolane, 2-fluoropropyl sulfolane, 2-fluoro ethyl sulfolane, 4,5-dihydro-3 methyl thiophene 1,1-dioxide, 3,4-epoxy thiophane-1, the 1-dioxide, 2-methyl thiophane 1, the 1-dioxide, thiophane-3-alcohol-1, the 1-dioxide, the 3-cyclobufene sultone, 2,4-dimethyl-3-cyclobufene sultone, trans-3,4-dihydroxy thiophane-1, the 1-dioxide, 3-chloro-2,5-dihydro-thiophene-1, the 1-dioxide, N, N-dimethyl tetrahydro-3-thiophenine 1, the 1-dioxide, 4-chloro-1,1-dioxo-thiophane-3-alcohol, 2,3-dihydro-3-thiocyanates thiophene-1,1-dioxide etc.
These sulfolane and derivative thereof can use a kind or will be more than 2 kinds mix and use.
The content that contains thing that comprises at least one side of sulfolane and derivative thereof with respect to the total amount of electrolyte composition, is 5 quality %～40 quality %, is preferably 8 quality %～25 quality %, is preferably 10 quality %～20 quality % especially.This content that contains thing during less than 5 quality %, can't obtain enough additive effects with respect to the total amount of electrolyte composition.On the other hand, when this content that contains thing surpasses 40 quality % with respect to the total amount of electrolyte composition, can't wish the increase of additive effect, the worry of the volatilization progress of opposite solvent increases.
The reason of the preferred 8 quality % of the content that contains thing～25 quality % that comprises at least one side of sulfolane and derivative thereof is, if the viscosity that in this scope, then can obtain this content that contains thing to realize simultaneously reduces the increase of the initial performance that produces and suppresses the two effect of durability that volatilization causes.In addition, this reason that contains preferred especially 10～20 quality % of content of thing is, can obtain to realize simultaneously that further viscosity reduces the increase of the initial stage characteristic that produces and suppresses the two effect of durability that volatilization causes.
Electrolyte composition of the present invention can add the redox couple that is not neccessary composition.When electrolyte composition of the present invention is applicable to dye-sensitized solar cell etc., preferably add redox couple.
As redox couple, be not particularly limited, preferably use by iodide ion (I
-), bromide ion (Br
-), chloride ion (Cl
-) wait halide ion and I
3 -, I
5 -, I
7 -, Br
3 -, Cl
2I
-, ClI
2 -, Br
2I
-, BrI
2 -The halogen of forming in the polyhalide ion is a redox couple.
This halogen is a redox couple, for example can by add iodine/iodide ion, bromine/bromide ion etc. to obtaining as redox couple.As the supply source of iodide ion or bromide ion, can use lithium salts, season imidazole salts, 4-butyl ammonium etc. independent or compoundly.
In the electrolyte composition of the present invention, in the scope of the proterties of not destroying electrolyte composition, characteristic, can add various additives, solvents such as tert .-butylpyridine, N-tolimidazole, guanidinesalt as required.
In the electrolyte composition of the present invention, as required by suitably adding high-molecular gel agent, low molecular gel agent, various nano particle, the agent of carbon nano-tube isogel, also can doubtful solidification, make so-called gel electrolyte.In addition, when making electrolyte composition of the present invention, preferably in clean room, in the glove box, carry out under the dry condition etc., impurity such as foreign matter, water are removed.
Above-mentioned electrolyte composition for example, is preferably used as the electrolyte that uses in the photo-electric conversion elements such as dye-sensitized solar cell.
Under the situation of the solvent that uses in the electrolyte composition in the past, the viscosity height, the initial performance of element can't improve, perhaps durability deficiency, therefore follow the process of time, electrolytical conductivity descends, and has the problem of the light transfer characteristic variation of photo-electric conversion element.To this, for above-mentioned electrolyte composition, shown in the embodiment described as follows, initial performance and durability are good.The electrolyte composition of initial performance height and excellent in te pins of durability all can be provided in liquid and gelatinous system in addition.
At this, the index (hereinafter referred to as the initial performance index) of expression initial performance is that the initial value (initial stage conversion efficiency B) of photoelectric conversion efficiency that becomes the electrolyte composition of object is that the ratio of initial value (benchmark initial stage conversion efficiency A) of the photoelectric conversion efficiency of 1-hexyl-3-methylimidazole iodide (following table is shown HMImI) and the electrolyte composition that does not add solvent multiply by 100 values that obtain (initial performance value C) with respect to making ionic liquid in this specification.If the formula of being expressed as then is initial performance value C=initial stage conversion efficiency B/ benchmark initial stage conversion efficiency A * 100.
The index (hereinafter referred to as durability index) of expression durability is that the electrolyte composition that becomes object remains in 85 ℃ the thermostat through the measured value (conversion efficiency D after 1000 hours) of the photoelectric conversion efficiency measured after 1000 hours and multiply by 100 and the value (durability performance value E) that obtains with respect to the ratio of said reference initial stage conversion efficiency A.If the formula of being expressed as then is conversion efficiency D/ benchmark initial stage conversion efficiency A * 100 of durability performance value after E=1000 hour.And durability performance value E multiply by 100 and the value that obtains also becomes the durable change rate F of expression durability index with respect to the ratio of above-mentioned initial performance value C.If the formula of being expressed as then is durability performance value F=durability performance value E/ initial performance value C * 100.
Above-mentioned electrolyte composition also can be gel, so when manufacturing process, battery breakage etc., even electrolyte composition exposes and also can not worry to leak out (leak of liquid), productivity, the property handled excellence.
Secondly, the embodiment to the photo-electric conversion element that used above-mentioned electrolyte composition describes.
Fig. 1 is the execution mode as photo-electric conversion element of the present invention, the sectional view of the summary configuration example of expression dye-sensitized solar cell.
This dye-sensitized solar cell 1, on transparent electrode substrate 2, possess the effect utmost point 6 and with the setting of this effect utmost point 6 subtends to electrode 8, this effect utmost point 6 have by oxide semiconductor particulates such as titanium oxide constitute and appendix the oxide semiconductor perforated membrane 5 of light sensitizing coloring matter, these the effect utmost points 6 and to electrode 8 between be formed with the dielectric substrate 7 of having filled above-mentioned electrolyte composition.
Transparent electrode substrate 2 has formed the conductive layer 3 that is made of electric conducting material on transparent bases such as glass plate, plastic sheet 4.
Material as transparent base 4, the high material of preferred light transmittance on purposes, except glass, can also use for example PETG (PET), PEN (PEN), Merlon (PC), polyether sulfone transparent plastic sheets such as (PES) etc.
As conductive layer 3, from the viewpoint of the light transmission of transparent electrode substrate 2, preferred indium oxide (ITO), the tin oxide (SnO that adds tin that use individually
2), add the tin oxide transparent oxide semiconductors such as (FTO) of fluorine, perhaps with they multiple compound uses.But, be not particularly limited in these, from the viewpoint of light transmission and conductivity, can select to use the suitable material that is fit to application target.In addition, in order to improve the current collecting efficiency of generation current, can be with the area occupation ratio of the scope of the light transmission that significantly do not destroy transparent electrode substrate 2 and the metallic wiring layer that constitutes with gold, silver, platinum, aluminium, nickel, titanium etc.When using metallic wiring layer, can be configured to arbitrary shapes such as clathrate, striated, pectination, to obtain the balance of current collecting efficiency and incident light quantity.
As the method that forms conductive layer 3, can use the known proper method of the material of corresponding conductive layer 3.For example, when forming conductive layer 3, can enumerate film forming methods such as sputtering method, CVD method, SPD method (spraying the thermal decomposition method of piling), vapour deposition method by oxide semiconductors such as ITO, FTO.Conductive layer 3 is considered transmitance and conductivity, forms the thickness about 0.05 μ m～2.0 μ m usually.
Oxide semiconductor perforated membrane 5 is with titanium dioxide (TiO
2), tin oxide (SnO
2), tungsten oxide (WO
3), zinc oxide (ZnO), niobium oxide (Nb
2O
5) the oxide semiconductor particulate with average grain diameter 1～1000nm that is composited more than a kind or 2 kinds that waits is that principal component, thickness are the porous membrane about 0.5～50 μ m.
As the method that forms oxide semiconductor perforated membrane 5, applicable for example following method: for the colloidal solution of dispersion liquid that commercially available oxide semiconductor microparticulate is formed in required decentralized medium or the modulation of employing sol-gel process, after adding required additive as required, adopt known method such as silk screen print method, ink jet printing method, rolling method, scraper plate method, spin-coating method, spraying process to be coated with, carry out drying, burn till.As the formation method beyond this, applicablely for example electrode base board 2 be impregnated in the colloidal solution, adopt electrophoresis to make the oxide semiconductor particulate be attached to electrophoresis galvanoplastic on the electrode base board 2, blowing agent is mixed in after colloidal solution, dispersion liquid is coated with, carries out sintering and method of porous etc.
There is no particular restriction for the sensitizing coloring matter of appendix on oxide semiconductor perforated membrane 5, can be according to the material of purposes, oxide semiconductor perforated membrane, from for example to have ruthenium complex, the iron complex of the part that comprises bipyridine structure, terpyridyl structure etc., the metal complex of porphyrin system, phthalocyanine system is representative, suitably selects in the derivative of organic pigments such as eosin, rhodamine, merocyanine, cumarin etc. to use.
As to electrode 8, can use the product that for example on the substrate that constitutes by non-conductive materials such as glass, has formed the film that constitutes by electroconductive oxide semiconductors such as ITO, FTO, perhaps on substrate with conductive material evaporation, coatings etc. such as gold, platinum, carbon-based materials, thereby formed the product of electrode.In addition, also can be the product that on the semi-conductive film of electroconductive oxides such as ITO, FTO, has formed the layer of platinum, carbon, electroconductive polymer etc.
As making such method to electrode 8, for example can enumerate and behind the coating chloroplatinic acid, heat-treat, thus the method for formation platinum layer.Perhaps can be to adopt vapour deposition method, sputtering method on substrate, to form the method for platinum layer.
Method as form the dielectric substrate 7 that is made of above-mentioned electrolyte composition on the effect utmost point 6 is not particularly limited, and can enumerate the method for the above-mentioned electrolyte composition that for example at every turn drips on a small quantity on the effect utmost point 6.Perhaps, also can form dielectric substrate 7 by at the effect utmost point 6 or first-class with the electrolyte coating etc. to electrode 8.And then, also can be to utilize capillarity etc. to fill the method etc. of above-mentioned electrolyte composition in two interelectrode gaps.Adopt these methods, electrolyte composition is impregnated in the space of oxide semiconductor perforated membrane 5 and fills.
The photo-electric conversion element of the present invention that the above obtains, the solvent that constitutes electrolyte composition comprises at least one side's of containing sulfolane and derivative thereof the thing that contains, total amount with respect to electrolyte composition, this content that contains thing is 5 quality %～40 quality %, so excellent in te pins of durability, when being used for the photo-electric conversion element of dye-sensitized solar cell etc., electrolytical rotten, the loss that does not exist the volatilization etc. of solvent to cause, can realize the initial performance height, and the light transfer characteristic of excellent in te pins of durability.In addition, be gel if make electrolyte composition, the then leakage of electrolyte from the gap of container etc., the scattering when photo-electric conversion element is damaged etc. are inhibited, and compare when having used aqueous electrolyte, become more excellent photo-electric conversion elements such as durability.
In addition, the dye-sensitized solar cell that uses photo-electric conversion element of the present invention to make, electrolytical rotten, the loss that does not exist the volatilization etc. of solvent to cause can realize the initial performance height, and the light transfer characteristic of excellent in te pins of durability.In addition, if making electrolyte composition is gel, the then leakage of electrolyte from the gap of container etc., the scattering when photo-electric conversion element is damaged etc. are inhibited, and compare when having used aqueous electrolyte, become more excellent dye-sensitized solar cells such as durability.
Embodiment
[embodiment 1～16]
The modulation of＜aqueous electrolyte composition 〉
Use 1-hexyl-3-methylimidazole iodide (HMImI) as ionic liquid, the iodine of dissolving 0.45M, the guanidine thiocyanate of 0.1M, the N-tolimidazole of 0.5M in this ionic liquid, thus modulation contains the electrolyte of iodine/iodide ion as redox couple.
In above-mentioned electrolyte, add sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, 2 respectively as solvent, 4-dimethyl-3-sulfolane, 3-hydroxyl sulfolane, 3-cyclobufene sultone, 2,4-dimethyl-3-cyclobufene sultone obtains the electrolyte composition of embodiment 1～16 so that the content of any is as shown in table 1 with respect to the electrolyte composition total amount.
In this electrolyte composition, as insignificant impurity, water etc. contain less than 1% with respect to the electrolyte composition total amount.
The making of the photo-electric conversion element that＜embodiment relates to 〉
On the surface of the FTO of the glass substrate that has FTO film film (conductive layer) side, adopt silk screen printing coating titanium oxide paste (PST21NR, catalyst change into industrial society system), dry back is 500 ℃ of following heat treated 1 hour, thereby formed titanium dioxide porous electrode.It is flooded more than 24 hours in the solution that contains ruthenium complex (N719 pigment), make the sensitizing coloring matter appendix, the making effect utmost point to the TiO 2 particles surface.
In addition, as to electrode, prepare to adopt sputtering method to be provided with the FTO glass electrode substrate of the catalyst layer that constitutes by platinum.
At the effect utmost point with between to electrode, dispose the hot melt sheet material (Himilan, Mitsui-DuPont Polychemical corporate system) of thick 30 μ m, will act on the utmost point and to electrode adhesion.
From the electrolyte inlet, inject the above-mentioned electrolyte composition of embodiment 1～16 respectively and form dielectric substrate at the effect utmost point with between electrode, the sealing inlet is made the dye-sensitized solar cell that becomes test cell.
Should illustrate that the injection of electrolyte composition, sealing are all carried out in the glove box below amount of moisture is controlled to be 1ppm.
[comparative example 1～6]
The modulation of＜aqueous electrolyte composition 〉
Modulate electrolyte similarly to Example 1.
Add the sulfolane shown in the table 1, gamma-butyrolacton or propylene carbonate respectively as solvent in this electrolyte, any content is as described in Table 1 with respect to the electrolyte composition total amount, obtains the electrolyte composition of comparative example 1-6.In this electrolyte composition, as insignificant impurity, water etc. contain less than 1% with respect to the electrolyte composition total amount.
The making of the photo-electric conversion element that＜comparative example 1～6 is related 〉
Form except injecting the above-mentioned electrolyte composition of comparative example 1～6 dielectric substrate, make the dye-sensitized solar cell that becomes test cell similarly to Example 1 at the effect utmost point with between to electrode.
The light transfer characteristic of＜test cell 〉
As mentioned above, for each test cell (embodiment 1～16 and comparative example 1～6) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 1.
[table 1]
[embodiment 17]
Except using 1-propyl group-3-methylimidazole iodide (following table is shown PMImI), make electrolyte composition and the dye-sensitized solar cell that becomes test cell similarly to Example 4 as the ionic liquid.
[comparative example 7]
Except using PMImI, similarly make electrolyte composition and the dye-sensitized solar cell that becomes test cell with comparative example 1 as the ionic liquid.
As mentioned above, for each test cell (embodiment 17 and comparative example 7) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 2.
[table 2]
[embodiment 18]
Except using two (trifluoromethyl sulfonyl) acid imides (following table is shown EMImFSI) of 1-ethyl-3-methylimidazole, make electrolyte composition and the dye-sensitized solar cell that becomes test cell similarly to Example 4 as the ionic liquid.
[comparative example 7]
Except using EMImFSI, similarly make electrolyte composition and the dye-sensitized solar cell that becomes test cell with comparative example 1 as the ionic liquid.
As mentioned above, for each test cell (embodiment 18 and comparative example 8) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 3.
[table 3]
[embodiment 19]
Except using PMImI and 1-ethyl-3-methylimidazole four cyano borate (following table is shown EMImTCB) with PMImI: EMImTCB=6: the product of 4 mixed (following table is shown PMImI+EMImTCB) is as the ionic liquid, makes electrolyte composition similarly to Example 4 and becomes the dye-sensitized solar cell of test cell.
[comparative example 9]
Except using PMImI+EMImTCB, similarly make electrolyte composition and the dye-sensitized solar cell that becomes test cell with comparative example 1 as the ionic liquid.
As mentioned above, for each test cell (embodiment 19 and comparative example 9) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 4.
[table 4]
[embodiment 20]
Except using EIMImFSI and 1-ethyl-3-methylimidazole sulfovinate (following table is shown EMImEtS) with EIMImFSI: EMImEtS=6: 4 product of mixing (following table is shown EIMImFSI+EMImEtS) are as the ionic liquid, make electrolyte composition similarly to Example 4 and become the dye-sensitized solar cell of test cell.
[comparative example 10]
Except using EIMImFSI+EMImEtS, similarly make electrolyte composition and the dye-sensitized solar cell that becomes test cell with comparative example 1 as the ionic liquid.
As mentioned above, for each test cell (embodiment 20 and comparative example 10) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 5.
[table 5]
[embodiment 21, comparative example 11]
The modulation of＜gelatinous electrolyte composition 〉
Modulate electrolyte similarly to Example 1.
Add sulfolane as solvent in this electrolyte, make the total amount with respect to electrolyte composition, the content of sulfolane is the value shown in the table 6.And then with the total amount with respect to electrolyte composition, silicon dioxide (SiO
2) content of nano particle is that the mode of 5 quality % adds, and makes the electrolyte composition of accurate solidified (gelatinous) embodiment 21 and comparative example 11.
The making of＜photo-electric conversion element 〉
In order in effect extremely, to form dielectric substrate, each electrolyte composition with solidified the foregoing description 21 of standard and comparative example 11 is applied on the oxide semiconductor perforated membrane of the effect utmost point respectively, and then make and above-mentioned electrode is overlapped, encapsulate, in addition, make the dye-sensitized solar cell of the test cell of the test cell become embodiment 21 and comparative example 11 similarly to Example 1 respectively.
The light transfer characteristic of＜test cell 〉
As mentioned above, for each test cell (embodiment 21 and comparative example 11) of making,, measure initial performance value C, durability performance value E and durable change rate F based on above-mentioned initial performance index and above-mentioned durability index.
Show the result in table 6.
[table 6]
By the result of table 1～6 as can be known, used electrolyte composition of the present invention, promptly in each solion (HMImI, PMImI, EMImFSI, PMImI+EMImITCB, EIMImFSI+EMImEtS), use the sulfolane or derivatives thereof, with respect to the electrolyte composition total amount, the content of sulfolane or derivatives thereof is the test cell of the embodiment 1～21 of the electrolyte composition that 5 quality % are above, 40 quality % are following, compare with comparative example 1～11 respectively, obtain good initial performance and durability.
In addition, as shown in Table 1, if with respect to the total amount of electrolyte composition, the content of sulfolane is less than 5 quality %, and then effect reduces.
The making of＜large-area photo-electric conversion element 〉
Surface in FTO film (conductive layer) side of the glass substrate of the band FTO of 140mm * 140mm film, adopt silk screen printing coating titanium oxide to stick with paste (PST21NR, catalyst change into industrial society system), after the drying,, thereby form the titanium oxide porous layer 500 ℃ of following heat treated 1 hour.On substrate, formed simultaneously the current collection distribution that the printed circuit by silver constitutes.Making the circuit of this current collection distribution wide is 300 μ m, and making thickness is 10 μ m.The corrosion that causes for fear of iodine electrolyte is with the compact protective film silver-colored distribution that is covered.By it is flooded more than 24 hours in the solution that contains ruthenium complex (N719 pigment), make the sensitizing coloring matter appendix on the TiO 2 particles surface, the making effect utmost point.
In addition, as to electrode, the catalyst layer of preparing to adopt sputtering method on the titanium foil of thick 40 μ m, to be provided with and constituting by platinum to electrode.
In order to form dielectric substrate in effect on extremely, each electrolyte composition with solidified the foregoing description 21 of standard and comparative example 11 is coated on the oxide semiconductor perforated membrane of the effect utmost point respectively, makes above-mentioned electrode to be overlapped again, and encapsulates.Adopt above order, make the dye-sensitized solar cell of the test cell of the test cell that becomes embodiment and comparative example respectively.
Have, the injection of electrolyte composition, encapsulation are all carried out in the glove box that amount of moisture is controlled to be below the 1ppm again.
The light transfer characteristic of＜test cell 〉
Measure the light transfer characteristic of the test cell of making as mentioned above.
For this test cell, measure the initial value (initial stage conversion efficiency) of photoelectric conversion efficiency and in 85 ℃ thermostat, keep and, compare to initial value with through the value after 1000 hours through the photoelectric conversion efficiency after 1000 hours.
Its result for the test cell of this embodiment, obtains good output, stability.
As can be known from the above results, in the system of aqueous electrolyte composition and gelatinous electrolyte composition, at least one side's of containing sulfolane and derivative thereof contain thing as solvent owing to all be to use, total amount with respect to electrolyte composition, this content that contains thing is the electrolyte composition of 5 quality %～40 quality %, even when therefore electrolyte composition of the present invention being applied to large-area photo-electric conversion element, also can obtain stable properties.
In addition, if that uses at least one side contain sulfolane and derivative thereof contains thing as solvent, total amount with respect to electrolyte composition, this content that contains thing is the electrolyte composition of 8 quality %～25 quality %, can obtain as can be known to realize simultaneously viscosity descend the initial performance that produces increase and suppress these two kinds of effects of the durability that volatilization produces.
In addition, if that uses at least one side contain sulfolane and derivative thereof contains thing as solvent, total amount with respect to electrolyte composition, this content that contains thing is the electrolyte composition of 10 quality %～20 quality %, can obtain as can be known to realize simultaneously further viscosity descend the initial performance that produces increase and suppress these two kinds of effects of the durability that volatilization produces.That is, confirmed the validity that electrolyte composition of the present invention produces.
Utilize possibility on the industry
Electrolyte composition of the present invention can be preferably used as the electrolyte that uses such as in the photo-electric conversion elements such as dye-sensitized solar cell. In addition, expectation can be used as the electrolyte of the various elements with electricity or electrochemical action.
Claims (2)
1. electrolyte composition, it is characterized in that, be the electrolyte composition that contains ionic liquid and solvent, and above-mentioned solvent comprises at least one side's of containing sulfolane and derivative thereof the thing that contains, with respect to the total amount of this electrolyte composition, this content that contains thing is 5 quality %～40 quality %.
2. a photo-electric conversion element is characterized in that, possesses the described electrolyte composition of claim 1 as electrolyte.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-311352 | 2007-11-30 | ||
| JP2007311352 | 2007-11-30 | ||
| PCT/JP2008/071673 WO2009069757A1 (en) | 2007-11-30 | 2008-11-28 | Electrolytic composition and photoelectric conversion element using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101878559A true CN101878559A (en) | 2010-11-03 |
Family
ID=40678646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880118419XA Pending CN101878559A (en) | 2007-11-30 | 2008-11-28 | Electrolytic composition and photoelectric conversion element using the same |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US8257615B2 (en) |
| EP (1) | EP2219260B1 (en) |
| JP (1) | JP5075913B2 (en) |
| KR (1) | KR20100049680A (en) |
| CN (1) | CN101878559A (en) |
| AU (1) | AU2008330576B2 (en) |
| TW (1) | TW200933957A (en) |
| WO (1) | WO2009069757A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113169379A (en) * | 2019-03-05 | 2021-07-23 | 株式会社日立制作所 | Nonaqueous electrolyte solution, semisolid electrolyte layer, sheet for secondary battery, and secondary battery |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200933957A (en) * | 2007-11-30 | 2009-08-01 | Fujikura Ltd | Electrolyte composition and photoelectric conversion element using the same |
| TW201141816A (en) * | 2010-01-15 | 2011-12-01 | Ube Industries | Photochemical cell including semiconductor fine particles sensitized by binuclear ruthenium complex dye, and electrolyte solution that contains ammonium salt compound or phosphonium salt compound |
| FR2956208B1 (en) * | 2010-02-05 | 2012-04-27 | Centre Nat Rech Scient | METHOD FOR NON-CONTACT DETERMINATION OF CHARACTERISTICS OF A PHOTOCONVERTER |
| JP5655187B2 (en) | 2010-07-27 | 2015-01-21 | 島根県 | Dye-sensitized solar cell and method for preventing catalyst elution from catalyst electrode |
| JP2012084374A (en) * | 2010-10-12 | 2012-04-26 | Sony Corp | Photoelectric conversion element, manufacturing method therefor, electrolyte layer for photoelectric conversion element and electronic apparatus |
| WO2012105578A1 (en) * | 2011-01-31 | 2012-08-09 | 宇部興産株式会社 | Photochemical cell comprising semiconductor microparticles sensitized by binuclear ruthenium complex dye, and comprising electrolyte solution that contains tetraaryl borate compound or electrolyte solution that contains multiple types of onium salt |
| JP2013206681A (en) * | 2012-03-28 | 2013-10-07 | Osaka Gas Co Ltd | Electrolyte for dye-sensitized solar cell having high performance and high durability |
| WO2014084296A1 (en) | 2012-11-30 | 2014-06-05 | 日本化薬株式会社 | Dye-sensitized solar cell |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH674596A5 (en) | 1988-02-12 | 1990-06-15 | Sulzer Ag | |
| JP4124487B2 (en) * | 1996-12-30 | 2008-07-23 | イドロ―ケベック | Five-membered ring anion salts or tetraazapentalene derivatives and their use as ion-conducting substances |
| US20050045851A1 (en) * | 2003-08-15 | 2005-03-03 | Konarka Technologies, Inc. | Polymer catalyst for photovoltaic cell |
| US7220914B2 (en) * | 2003-12-01 | 2007-05-22 | Konarka Technologies, Inc. | Zwitterionic compounds and photovoltaic cells containing same |
| JP4008669B2 (en) | 2001-03-22 | 2007-11-14 | 株式会社東芝 | Photosensitized solar cell |
| US6552843B1 (en) * | 2002-01-31 | 2003-04-22 | Innovative Technology Licensing Llc | Reversible electrodeposition device with ionic liquid electrolyte |
| JP2004087387A (en) * | 2002-08-28 | 2004-03-18 | Nisshinbo Ind Inc | Electrolyte composition and photoelectrochemical cell |
| US7193764B2 (en) * | 2003-10-08 | 2007-03-20 | Gentex Corporation | Reversible electrodeposition devices and associated electrochemical media |
| JP4820535B2 (en) * | 2004-02-24 | 2011-11-24 | 弘幸 大野 | New imidazolium compounds |
| JP5089381B2 (en) | 2005-04-11 | 2012-12-05 | 日本化薬株式会社 | Electrolyte composition for photoelectric conversion element and photoelectric conversion element using the same |
| WO2007055392A1 (en) * | 2005-11-11 | 2007-05-18 | Nippon Shokubai Co., Ltd. | Ionic compound |
| JP2007250473A (en) * | 2006-03-17 | 2007-09-27 | Sanyo Chem Ind Ltd | Gel-like composition |
| JP5000162B2 (en) * | 2006-03-22 | 2012-08-15 | Ｊｘ日鉱日石エネルギー株式会社 | Dye-sensitized solar cell |
| JP4948029B2 (en) * | 2006-04-26 | 2012-06-06 | Ｊｘ日鉱日石エネルギー株式会社 | Dye-sensitized solar cell |
| TW200933957A (en) * | 2007-11-30 | 2009-08-01 | Fujikura Ltd | Electrolyte composition and photoelectric conversion element using the same |
-
2008
- 2008-11-28 TW TW097146294A patent/TW200933957A/en unknown
- 2008-11-28 JP JP2009513909A patent/JP5075913B2/en active Active
- 2008-11-28 AU AU2008330576A patent/AU2008330576B2/en not_active Ceased
- 2008-11-28 KR KR1020107006992A patent/KR20100049680A/en not_active Application Discontinuation
- 2008-11-28 CN CN200880118419XA patent/CN101878559A/en active Pending
- 2008-11-28 EP EP08855353.2A patent/EP2219260B1/en not_active Not-in-force
- 2008-11-28 WO PCT/JP2008/071673 patent/WO2009069757A1/en active Application Filing
-
2010
- 2010-05-27 US US12/789,135 patent/US8257615B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113169379A (en) * | 2019-03-05 | 2021-07-23 | 株式会社日立制作所 | Nonaqueous electrolyte solution, semisolid electrolyte layer, sheet for secondary battery, and secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009069757A1 (en) | 2009-06-04 |
| EP2219260A1 (en) | 2010-08-18 |
| TW200933957A (en) | 2009-08-01 |
| JPWO2009069757A1 (en) | 2011-04-21 |
| EP2219260A4 (en) | 2011-03-09 |
| AU2008330576A1 (en) | 2009-06-04 |
| US20100233531A1 (en) | 2010-09-16 |
| AU2008330576B2 (en) | 2012-01-12 |
| EP2219260B1 (en) | 2015-11-04 |
| KR20100049680A (en) | 2010-05-12 |
| US8257615B2 (en) | 2012-09-04 |
| JP5075913B2 (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101878559A (en) | Electrolytic composition and photoelectric conversion element using the same | |
| JP4579160B2 (en) | Electrolyte composition, photoelectric conversion device using the same, and dye-sensitized solar cell | |
| KR101141776B1 (en) | Method for producing electrode substrate, electrode substrate, photoelectric converter and dye-sensitized solar cell | |
| Ahmad et al. | Efficient platinum‐free counter electrodes for dye‐sensitized solar cell applications | |
| Matsui et al. | Application of an ionic liquid-based electrolyte to a 100mm× 100 mm sized dye-sensitized solar cell | |
| Maiaugree et al. | Optimization of TiO2 nanoparticle mixed PEDOT–PSS counter electrodes for high efficiency dye sensitized solar cell | |
| CN101861677B (en) | Electrode substrate for photoelectric conversion device, method for manufacturing electrode substrate for photoelectric conversion device, and photoelectric conversion device | |
| CN102725905B (en) | Used by dye sensitization solar battery electrolyte and the DSSC that make use of this electrolyte | |
| Shen et al. | Quasi-solid-state dye-sensitized solar cells based on gel electrolytes containing different alkali metal iodide salts | |
| KR100837367B1 (en) | Electrolyte composition and photoelectric converter using same | |
| CN101228660A (en) | Electrode substrate and photoelectric conversion element | |
| Lu et al. | Quasi-solid-state dye-sensitized solar cells with cyanoacrylate as electrolyte matrix | |
| CN101868882A (en) | Electrode substrate for photoelectric conversion element | |
| JP5139501B2 (en) | Electrolyte composition for dye-sensitized solar cell and dye-sensitized solar cell using the same | |
| CN102891009A (en) | Nanoparticle having imidazolium salt chemically bound thereto, method of preparing the same, and nanogel electrolyte for dye-sensitive solar cell comprising the same | |
| Lan et al. | Durability test of PVP‐capped Pt nanoclusters counter electrode for highly efficiency dye‐sensitized solar cell | |
| AU2004303035A1 (en) | Electrolyte composition and photoelectric converter using same | |
| JP2012253004A5 (en) | ||
| JP4522673B2 (en) | Electrolyte composition, photoelectric conversion device using the same, and dye-sensitized solar cell | |
| Lee et al. | A comparative study of charge transport in quasi-solid state dye-sensitized solar cells using polymer or nanocomposite gel electrolytes | |
| CN105551834A (en) | Low-temperature and low-pressure preparation method of flexible dye-sensitized solar cell | |
| Lee et al. | Enhanced photovoltaic performance and long-term stability of dye-sensitized solar cells by incorporating SiO2 nanoparticles in binary ionic liquid electrolytes | |
| CN100438206C (en) | Electrolyte compositon, photoelectric converter and dye-sensitized solar cell using same | |
| CN102576922B (en) | Dye-sensitized solar cell and module thereof and dielectric substrate formation coating fluid | |
| JP2004327226A (en) | Electrode substrate and photoelectric conversion element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101103 |